TWI343143B - Non-perfluorinated resins containing ionic or ionizable groups and products containing the same - Google Patents

Non-perfluorinated resins containing ionic or ionizable groups and products containing the same Download PDF

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TWI343143B
TWI343143B TW093102930A TW93102930A TWI343143B TW I343143 B TWI343143 B TW I343143B TW 093102930 A TW093102930 A TW 093102930A TW 93102930 A TW93102930 A TW 93102930A TW I343143 B TWI343143 B TW I343143B
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Taiwan
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polymer
perfluorinated
acrylic
polyelectrolyte
group
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TW093102930A
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Chinese (zh)
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TW200418226A (en
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Lotfi Hedhli
Isabelle Decker
Holger Ernst Amort
Jyotsna Iyer
Scott Richard Gaboury
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Atofina Chem Inc
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Publication of TWI343143B publication Critical patent/TWI343143B/en

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    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47F—SPECIAL FURNITURE, FITTINGS, OR ACCESSORIES FOR SHOPS, STOREHOUSES, BARS, RESTAURANTS OR THE LIKE; PAYING COUNTERS
    • A47F8/00—Dummies, busts or the like, e.g. for displaying garments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47F—SPECIAL FURNITURE, FITTINGS, OR ACCESSORIES FOR SHOPS, STOREHOUSES, BARS, RESTAURANTS OR THE LIKE; PAYING COUNTERS
    • A47F13/00—Shop or like accessories
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • B01D69/14111—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix with nanoscale dispersed material, e.g. nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
    • B01D71/4011—Polymethylmethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B5/00—Joining sheets or plates, e.g. panels, to one another or to strips or bars parallel to them
    • F16B5/02—Joining sheets or plates, e.g. panels, to one another or to strips or bars parallel to them by means of fastening members using screw-thread
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/21—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/32—Use of chain transfer agents or inhibitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/42—Ion-exchange membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

A non-perfluoropolymer is described which contains at least one acrylic resin or vinyl resin having at least one ionic or ionizable group and optionally at least one additional polymer. Preferably, the polymers are useful in a variety of applications including in the formation of a membrane which is useful in batteries and fuel cells and the like. Methods of making the polymer blends are also described.

Description

玖、發明說明： 【發明所屬之技術領域】 本發月係合物樹脂’更特別地係關於包含離子及/ 或可離子化基之非全氟化聚合物樹㈣並相當於,,非全氣化 k電解貝）’其可用於各種產物中，h聚電解質隔膜及其 他熱塑性物品。本發明另關於製造這些樹脂以及利用這些 樹脂之方法。 【先前技術】 全氟碳離子交換隔膜提供高陽離子運送並已廣泛地用作 離子乂換隔膜。聚合物離子交換隔膜係相當於固體聚合物 電解質或聚合物交換隔膜(PEM)。因為迫切需要，最常用並 ° 商業A 1構付之隔膜係由全敗項酸化Nafion®及玖, invention description: [Technical field to which the invention pertains] The present invention is more specifically related to a non-perfluorinated polymer tree (IV) containing ions and/or ionizable groups and is equivalent to Gasification k electrolysis) can be used in a variety of products, h polyelectrolyte separators and other thermoplastics. The invention further relates to methods of making these resins and utilizing such resins. [Prior Art] Perfluorocarbon ion exchange membranes provide high cation transport and have been widely used as ion exchange membranes. The polymer ion exchange membrane is equivalent to a solid polymer electrolyte or a polymer exchange membrane (PEM). Because of the urgent need, the most commonly used and commercial A 1 constructed membranes are acidified Nafion® and

Aciplex®*合物製得。但是’報告及文獻描述這些隔膜運 作良好，但顯示數項限制阻礙商業化技術進一步發展◊另 外，其在氣態燃料的運作情m態燃料好，可能主要是 因為燃料交又污染而降低電池性能1膜㈣化學性及機 械強度疋燃料電池應用之重要性質。實際上，隔膜經常處 於尚差壓、吸水-脫水循環以及其他條件下。而且，當隔膜 是非常薄，如小於5〇微米時，機械強度變得重要。此外， 用於燃料電池或蓄電池應料，由於金屬離子的存在及偶 爾存在之溶劑，隔膜係處於可達20(TC之溫度下非常酸的媒 "裏氧化及/或還原環境中，這環境需要耐化學及耐電化學 以及熱安定之隔膜。 〇A90\90872 DOC4 -6- 1343143 目前，許多含氟隔膜具有下列缺點中之一或多項： I) 高液體及氣體交叉通過隔膜； II) 氟化聚合物與其他導致較差性質之聚合物間之異相 換合； Π1)在某些液體燃料的存在下耐化學性不夠； iv) 耐電化學性差； v) 磺酸化基缺乏異相分布； vi) 機械性質差；及/或 vii) 熱安定性差。 頒予Nora等人之美國專利第4,295,952號係關於陽離子隔 膜，其具有苯乙烯、二乙烯基苯與2-乙烯基吡啶、4-乙烯基 吡啶及/或丙烯酸中至少一種之部分磺酸化三聚物。 頒予Ehrenberg等人之美國專利第5,679 482號係關於摻 有含離子基之離子導電隔膜的燃料電池。形成隔臈之聚合 物包含已利用磺酸化試劑磺酸化之苯乙烯。磺酸化可以單 體或聚合物發生。 美國專利第5,795,668號描述一種含]^£八及利用1^0〇11™ 型聚合物之強化聚合物離子交換隔膜（pEM)的燃料電池。 PEM係以氟化多孔支撐層及當量為約5〇〇至2〇〇〇且較佳離 子交換容量為〇·5至2毫當量/克乾樹脂之強化離子交換隔膜 為基材。多孔支撐層係由特定PTFE及PTFE共聚物製成。隔 膜是側鏈包含_CF2CF2S〇3H之全氟化聚合物。由文獻已知 Nafion®型聚合物在甲醇燃料電池中可能有機械故障的問 題以及液體交又污染的問題。 0 \90\90872 D0C4 1343143 頒予Rusch之WO 97/41 168係關於一種多層離子交換複合 隔膜，其具有離子交換樹脂，如氟化或非氟化聚苯乙烯基 質之磺酸鹽及磺酸化聚四氟乙烯。 WO 98/205 73 A1描述一種含有高氟化鋰離子交換聚合物 電解質隔膜（PEM)之燃料電池。PEM係以浸泡非質子溶劑之 離子父換隔膜為基材。Made from Aciplex®. However, 'the report and the literature describe that these membranes work well, but show that several restrictions hinder the further development of commercial technology. In addition, its operation in gaseous fuels is good, probably because fuel exchange and pollution reduce battery performance. Membrane (4) Chemical and mechanical strength 重要 Important properties of fuel cell applications. In fact, the diaphragm is often subjected to differential pressure, water-dehydration cycles, and other conditions. Moreover, mechanical strength becomes important when the membrane is very thin, such as less than 5 microns. In addition, for fuel cells or battery materials, due to the presence of metal ions and occasional solvents, the diaphragm is in a very acid medium at a temperature of TC (oxidized and / or reduced in the environment), this environment A chemical resistant and electrochemically resistant and thermally stable membrane is required. 〇A90\90872 DOC4 -6- 1343143 Currently, many fluorine-containing membranes have one or more of the following disadvantages: I) high liquids and gases cross the membrane; II) fluorination Heterogeneous blending of polymers with other polymers that cause poorer properties; Π1) insufficient chemical resistance in the presence of certain liquid fuels; iv) poor resistance to electrochemistry; v) lack of heterogeneous distribution of sulfonating groups; vi) mechanical properties Poor; and / or vii) Poor thermal stability. U.S. Patent No. 4,295,952 to Nora, et al., which is directed to a cationic membrane having a partial sulfonated trimerization of at least one of styrene, divinylbenzene and 2-vinylpyridine, 4-vinylpyridine and/or acrylic acid. Things. U.S. Patent No. 5,679,482 to Ehrenberg et al. is directed to a fuel cell incorporating an ion-containing ion-conducting membrane. The polymer forming the barrier comprises styrene which has been sulfonated with a sulfonating reagent. Sulfonation can occur as a monomer or a polymer. U.S. Patent No. 5,795,668 describes a fuel cell comprising a reinforced polymer ion exchange membrane (pEM) using a 1^0〇11TM type polymer. The PEM is based on a fluorinated porous support layer and a reinforced ion exchange membrane having an equivalent weight of about 5 Torr to 2 Torr and a preferred ion exchange capacity of 〇 5 to 2 meq/g dry resin. The porous support layer is made of a specific PTFE and PTFE copolymer. The membrane is a perfluorinated polymer containing _CF2CF2S〇3H in its side chain. It is known from the literature that Nafion® type polymers may have mechanical failure problems and liquid cross-contamination problems in methanol fuel cells. 0 \90\90872 D0C4 1343143 WO 97/41 168 to Rusch is a multilayer ion exchange composite membrane having an ion exchange resin such as a sulfonate or sulfonated polycondensation of a fluorinated or non-fluorinated polystyrene matrix. Tetrafluoroethylene. WO 98/205 73 A1 describes a fuel cell comprising a lithium fluoride ion exchange polymer electrolyte membrane (PEM). PEM is based on an ion-exchanger separator that soaks an aprotic solvent.

WO 98/22989描述一種含有聚苯乙烯磺酸及聚（氟化亞乙 烯）之聚合物隔膜，其提供直接甲醇燃料電池（DMFC)用途 較低甲醇交叉污染。但是，所述聚合物摻合程序無法提供 可接受摻合物，而且磺酸化步驟複雜。WO 98/22989 describes a polymer membrane comprising polystyrene sulfonic acid and poly(ethylene fluoride) which provides direct methanol fuel cell (DMFC) use with lower methanol cross-contamination. However, the polymer blending procedure does not provide an acceptable blend and the sulfonation step is complicated.

Holmberg 等人（J. Material Chem.(1996 6(8), 1309))描述 藉由輻射接枝苯乙烯於PVDF薄膜上，接著以氣磺酸進行磺 酸化以製備質子導電隔膜。在本發明中，不需要磺酸化步 驟，因為磺酸化基可利用磺酸化單體摻入。Holmberg et al. (J. Material Chem. (1996 6(8), 1309)) describe the preparation of proton conductive membranes by graft grafting styrene onto a PVDF film followed by sulfonation with gas sulfonic acid. In the present invention, the sulfonation step is not required because the sulfonate group can be incorporated by the sulfonated monomer.

美國專利第6,252,000號係關於一種氟化離子交換/非官 能基聚合物之摻合物。特殊實例包括全氟化磺醯氟聚合物/ 聚（CTFE-共-全氟二氧戊環）摻合物。 WO 99/67304係關於一種磺酸化芳族全氟化單體與丙烯 酸系單體共聚合所製得之芳族全氟化離聚物。所存在的磺 酸化基係位於聚合物之氟化芳族鍵中。 美國專利第6,025,092號係關於一種全氟化離聚物，其中 VDF單體係與磺酸化單體聚合。 此外，描述續酸化丙稀酸系或績酸化乙稀系聚合物用於 ，例如超吸收體、尿布及隱形眼鏡（J. Meter. Chem. 1996, Ο \90V90872 DOC4 1343143 6(a)，1309及I0nic 3, 214(1997))。但是，未曾描述此類型產 物在用作聚電解質隔獏及類似物之隔膜方面的應用。將上 面及整個本申請案所提所有專利、公告案及申請案全文以-引用方式併入本文中並形成本申請案之一部分。 因此，有必要克服這些限制令之一或多項並發展一種可 用於液體燃料電池之隔膜。因此，有必須克服這些限制中 之一或多項並發展一種可用於液體燃料電池之隔膜。更特 別地，有必要發展一種非全氟化聚電解質以直接從水性或 非水性分散液製造隔膜。而且，有必要提供合成組合物及· 合成方法以及利用具有磺酸化或其他官能度之非全氟化聚 電解質之水或非水性分散液的方法。此外，有必要提供一 種車又令易且環保的方法。而且，熟諳此技者將偏好具有較- 向耐化學性及機械強度之聚電解質隔膜。而且，熟諳此技 者將偏好具有較高耐化學性及機械強度之聚電解質隔獏。 【發明内容】 因此，本發明一項特點係提供具有離子官能度之非全氟 化聚電解質。 霉 本發明另一項特點係提供一種具有高耐化學性及/或機 械強度之非全氟化聚電解質隔膜。 本發明另一項特點係提供可形成非全氟化聚電解質隔膜 之、’且伤的聚合物，其中該聚電解質隔膜可避免上述一或多 項缺點’如避免高液體交叉通過隔獏。 本發明另一項特點係提供可由聚合物分散液直接製得之 隔膜。 〇\9〇\90872.D〇C4 •9- 1343143 本發明另—項特點係提供非全氟化^:電解質而無另外績 酸化步驟。 — 為達到纟文具體化及廣泛描述之這些及其他優點並根據 本發明㈣，本發明係、關於—種含有至少—個丙稀酸系樹 脂及/或乙烯基樹脂之聚合物或聚合物摻合物，其中丙烯酸 系及/或乙烯基樹月旨具有至少一個離子或可離子化基，如磺 酸化基，其中聚合物的當量係從約200至約4,〇〇〇。 本發明也關於-種組合物，其包括摻合下列聚合物之聚合 物產物.a)至少一種具有丙烯酸系及/或乙烯基單位及至少一 個離子或可離子化基之聚合物；和…選用至少一種附加聚合 物’其中a)與b)S不同的。附加聚合物可為任何相容聚合物 ，如熱塑性聚合物（如熱塑性非氟聚合物或氟聚合物）。 本發明另關於一種組合物，其包含：勾至少一種含可聚 合丙烯酸系及/或含乙烯基之單體與至少一種含有至少一 個離子或可離子化基或兩者之單體在分散媒介的存在下之 聚合物產物，其中此聚合物的Ew係從約2〇〇至約4,〇〇〇，較 佳係從約200皇約1，400。 而且，本發明係關於一種製造上述組合物之較佳方法， 其包括至少一種含可聚合丙烯酸系及/或乙烯基之單體與 至少一種含有至少一個離子或可離子化基之單體在分散媒 介中進行聚合反應。 本發明另關於一種含有本發明聚合物或組合物之非全氟 化聚電解質隔膜，也關於含有本發明隔膜之燃料電池及 電池。 0 \90\90872 DOC4 -10· 1343143 而且， 並關於一 本發明係關於_ I rr- ^ '種包含上述隔膜之隔膜電極套 種利用此隔膜電極套組之燃料電池。 組 【實施方式】 全氟化聚電解質_係用於提供高陽離子運送並已廣泛 用作離子父換1¾膜q合物離子交換隔膜係相當於固體聚 &物電解貝或聚合物交換隔膜（pEM)。 最常用並可由商業公司購得之隔膜是Να〇η⑧及U.S. Patent No. 6,252,000 is directed to a blend of a fluorinated ion exchange/non-functional base polymer. Specific examples include perfluorinated sulfonium fluoropolymer/poly(CTFE-co-perfluorodioxolane) blends. WO 99/67304 relates to an aromatic perfluorinated ionomer obtained by copolymerizing a sulfonated aromatic perfluorinated monomer with an acrylic monomer. The sulfonating group present is located in the fluorinated aromatic bond of the polymer. U.S. Patent No. 6,025,092 is directed to a perfluorinated ionomer wherein a VDF single system is polymerized with a sulfonated monomer. Further, the description of the acidified acrylic acid or the acidified ethylene polymer is used, for example, in superabsorbents, diapers, and contact lenses (J. Meter. Chem. 1996, Ο \90V90872 DOC4 1343143 6(a), 1309 and I0nic 3, 214 (1997)). However, the use of this type of product as a separator for polyelectrolyte barriers and the like has not been described. All of the patents, publications, and applications filed in this application are hereby incorporated by reference in its entirety in its entirety herein in its entirety. Therefore, it is necessary to overcome one or more of these restrictions and develop a diaphragm that can be used in a liquid fuel cell. Therefore, it is necessary to overcome one or more of these limitations and develop a diaphragm that can be used in a liquid fuel cell. More specifically, it is necessary to develop a non-perfluorinated polyelectrolyte to fabricate a separator directly from an aqueous or non-aqueous dispersion. Moreover, it is necessary to provide synthetic compositions and methods of synthesis and methods of using water or non-aqueous dispersions of non-perfluorinated polyelectrolytes having sulfonation or other functionality. In addition, it is necessary to provide a car that is easy and environmentally friendly. Moreover, those skilled in the art will prefer polyelectrolyte membranes having more chemical resistance and mechanical strength. Moreover, those skilled in the art will prefer polyelectrolyte barriers with higher chemical and mechanical strength. SUMMARY OF THE INVENTION Accordingly, a feature of the present invention is to provide a non-perfluorinated polyelectrolyte having ionic functionality. Mold A further feature of the present invention is to provide a non-perfluorinated polyelectrolyte membrane having high chemical and/or mechanical strength. Another feature of the present invention is to provide a polymer that can form a non-perfluorinated polyelectrolyte membrane, wherein the polyelectrolyte membrane avoids one or more of the above disadvantages, such as avoiding high liquid crossover through the barrier. Another feature of the invention is the provision of a membrane which can be made directly from a polymer dispersion. 〇\9〇\90872.D〇C4 •9- 1343143 Another feature of the present invention is to provide a non-perfluorinated electrolyte: without additional acidification steps. - In order to achieve these and other advantages which are embodied and broadly described and in accordance with the invention (IV), the invention relates to a polymer or polymer blend containing at least one acrylic resin and/or vinyl resin A compound wherein the acrylic and/or vinyl group has at least one ionic or ionizable group, such as a sulfonate group, wherein the polymer has an equivalent weight of from about 200 to about 4, hydrazine. The invention also relates to a composition comprising a polymer product blended with the following polymers. a) at least one polymer having acrylic and/or vinyl units and at least one ion or ionizable group; At least one additional polymer 'where a) is different from b) S. The additional polymer can be any compatible polymer such as a thermoplastic polymer such as a thermoplastic non-fluoropolymer or a fluoropolymer. The invention further relates to a composition comprising: at least one monomer comprising a polymerizable acrylic and/or vinyl group and at least one monomer comprising at least one ion or ionizable group or both in a dispersion medium The polymer product is present, wherein the polymer has an Ew of from about 2 Torr to about 4, Torr, preferably from about 200 to about 1,400. Moreover, the present invention relates to a preferred process for the manufacture of the above composition comprising at least one monomer comprising a polymerizable acrylic and/or vinyl group and at least one monomer comprising at least one ion or ionizable group dispersed The polymerization is carried out in the medium. The invention further relates to a non-perfluorinated polyelectrolyte membrane comprising a polymer or composition of the invention, and to a fuel cell and battery comprising the membrane of the invention. 0 \90\90872 DOC4 -10· 1343143 Moreover, the invention relates to a fuel cell using the diaphragm electrode set of the diaphragm electrode comprising the above-mentioned separator for the _I rr-^' type. Group [Embodiment] Perfluorinated polyelectrolyte _ is used to provide high cation transport and has been widely used as an ion parent for the exchange of membranes. The ion exchange membrane system is equivalent to a solid poly & electrolysis shell or polymer exchange membrane ( pEM). The most commonly used and commercially available membranes are Να〇η8 and

Aci^ex®。但是，文獻中極少摇述非全氟化聚電解質隔膜 。這是由於隔膜的耐化學性、耐電化學性及機械強度是燃 料電池應用之重要性f的事實。實際上，隔膜經常處於高 差[下而且，S隔膜是非常薄（小於50微米）時，機械強度 變仔重要。用於燃料電池或蓄電池應用時，隔膜係處於可 達200t之溫度下非常酸的媒介中和金屬離子、溶劑和類似 物的存在下，因此需要高耐化學性以及耐電化學性。使用 齓化鹼時’因為氟化物質具有天生固有耐化學性及耐電化 學性’因此經常可符合這些要求。但是，這些隔膜顯示包 括，但不限於高溫（70、_200t：範圍）下機械性質差 '交又污染 及重複吸水-脫水循環後機械故障等限制。另外，製備這些 全氟化聚電解質需要數個步驟並包括造成高成本之化學程 序毛展谷易且便且的化學程序將進一步解決燃料電池商 業化的屏障。 本發明係關於一種非全氟化聚電解質，其包含至少一種 丙烯酸系及/或乙烯基樹脂或聚合物，其中此樹脂或聚合物 可有至少一個離子或可離子化基，如磺酸化及/或膦酸化基 O:\90\90872 DOC4 • 11- 1343143 丙烯酸系樹脂之混合物或可另外包含非丙烯酸系樹脂，如 乙烯基單體及苯乙烯系單體β ' 可用於非全氟化聚電解質之乙烯基單體實例包括，但不 限於苯乙烯、乙酸乙烯酯、乙烯基醚、乙烯基酯如購自shell 之VeoVa 9及Ve〇Va 1〇、丙烯酸乙烯酯、新戊酸乙烯酯、苯 甲酸乙烯酯、硬脂酸乙烯酯及類似物和其任何組合物。 此外’非全氟化聚電解質包含至少一個離子（如績酸鹽或 膦酸鹽）或可離子化基如磺酸化或膦酸化基或磺醯基。可離 子化基是一個可形成離子基之基團，如環狀胺基酸、礦内 8曰、順丁烯一酸針、硫醇、硫化物、ph〇Sphaiane及類似基 團。這些基團可藉任何方式如在一或多種含有離子或可離 子化基之單體的存在下摻合丙烯酸系及/或乙烯系樹脂成 為非全氟化聚電解質的一部分。在另一實例中，一或多種 用於形成非全氟化聚電解質之單體可包含離子或可離子化 基。 除了上述有關丙烯酸系及/或乙烯系樹脂之組份外，丙烯 西文糸及/或乙稀糸樹脂可另包含或另在一或多種附加單體 的存在下形成’只要這些單體可與整體形成之丙烯酸系及/ 或乙烯系樹脂相容，其中這些附加單體視情況具有任何官 能基類型。 如早先所述’最好丙烯酸系及/或乙烯系樹脂是數種單體 聚合的結果，其中之一包含離子或可離子化基，另一個係 包含丙烯酸系及/或乙烯系樹脂之丙烯酸系及/或乙烯系單 位。更佳係丙烯酸系及/或乙烯系樹脂係由（1)丙烯酸烷基酯 0 \90\908?2 D〇C4 -13- 1343143 體實例包括異丁基甲基丙烯醯胺、曱基丙烯酸去水甘油酯 、二甲基丙烯酸二乙二醇酯及三甲氧基矽烷甲基丙烯酸酯 。可能希望交聯以獲得較佳機械性質及耐溶劑性。 對於某些特定應用’可利用低分子量可共聚合聚合物或 募聚物。再者，使用丙烯酸烧基酯（1)與曱基丙烯酸烷基酯 (2)之混合物時，可適當地調整其比例以達到所需性質。 包含至少一個離子或可離子化基之單體（5)實例包括，但 不限於丙烯酿胺橫酸丙酯、乙烯基膦酸、乙稀基績酸、曱 基丙烯酸項酸丙酯、曱基丙稀酸項酸乙酯》較佳係使用這 些單體之酸型態或鹽衍生物。例如，在粒種乳化聚合中， 可在第一階段或第二階段或兩階段都摻入磺酸化單體。離 子基的含量最好係從約2 0 0至約2 5 0 0 E W，較佳係從約2 〇 〇 至約1100 EW，其中EW是當量，而且是每磺酸化單位之聚 合物克數。 本發明包含至少一種丙烯酸系或乙烯基樹脂或兩者之聚 合物中丙烯酸系或乙烯基樹脂相關當量最好係從約2〇〇至 約4,000 ’較佳係從約2〇〇至約ι，4〇〇，其中該聚合物具有至 少一個離子或可離子化基。此較佳當量範圍提供較佳隔膜 形成性質及避免氟聚合物需求之能力。本發明聚合物視情 況可以摻合物形式形成。較佳地，本發明聚合物係利用慣 用交聯技術進行交聯。 交聯可經由慣用方法完成，包括，但不限於自縮合、第 二交聯劑之添加或輻射交聯。這些係完整描述於文獻中並 為热知技術。可進行自縮合交聯之單體實例包括Ν_羥甲基 O:\90\90872. DOC4 -15- 丙烯醯胺、異丁氧基曱基丙烯醯胺、N -亞甲基雙丙烯醯胺 及曱基丙烯酸去水甘油酯。第二交聯劑實例包括異氰酸酯 、二聚氱胺、環氧化物、羧酸酯、烷氧基矽烷、矽酮、吖 %丙烷及碳二亞胺。輻射交聯之實例包括電子束、紫外光 及γ-射線。 s可水合乙烯基及/或丙烯酸系單體之混合物的聚合反 應可分開進行，然後與一或多種聚合物摻合在一起或在一 或多種聚合物的存在下進行聚合。含乙烯基及/或丙烯酸系 單體之聚合反應可藉溶液、整體、乳化聚合或任何其他已 知聚合方法達到。 若含可聚合乙烤基及/或丙婦酸系離子之單體混合物的 聚合反應是分開進行，然後與一或多種聚合物摻合在一起 ，此摻合可經由各種慣用方式進行，其包括，但不限於溶 液掺合、擠壓摻合、乳膠摻合及類似方法。對於溶液摻合 ’聚合物可溶解或分散在溶劑中。聚合物所用溶劑可類似 或異於含丙烯酸系/乙烯基離子之聚合物所用溶劑。例如， 摻合可包含兩種溶劑溶液/分散液或將粉末加入溶劑溶液/ 分散液中或兩種聚合物溶於相同溶劑或任何其他組合物中 。典型所用溶劑包括四氫呋喃、丙酮、二甲基亞硬、二曱 基甲酿胺、Ν-甲基吡咯酮。對於熔化擠壓摻合，典型擠壓 溫度範圍係介於約l〇〇t與約30(TC之間，較佳係從約yo °C至約250°C。材料可被擠壓成如顆粒或薄膜形狀。對於乳 膠掺合例子，可在數種慣用方式下產生混合：丙稀酸系/乙 烯基乳膠可與聚合物乳膠混合或丙烯酸系/乙稀基聚合物 〇\90\90872.DOC4 •16- 1343143 可分散或溶於聚合物乳膠中或任何其他已知混合方式a混 合可包含超過兩種乳膠。各乳膠之用量及性質係依獲得預 期物理及化學性質和獲得預期EW的方式調整。在水性隔膜 例子（如直接乳膠製得之例子）中，可針對所需性質調整一或 多種乳膠之粒徑及固體含量。 對於溶劑聚合反應，聚合反應可利用慣用技術發生。在 含有另一種聚合物之摻合物例子中，聚合物摻合物所用溶 劑可類似或異於丙烯酸系/乙烯基聚合物所用溶劑。例如， 摻合可包括兩種溶劑溶液/分散液或將粉末加入溶劑溶液/ 分散液中或兩種聚合物溶於相同溶劑或任何其他組合物中 典型所用；谷劑包括二曱基亞硬、二甲基甲酿胺、Ν·甲基 口比嘻明、異丙醇、甲醇及類似溶劑。 乳化聚合反應可在與慣用乳化聚合相同之條件下進行。 最好將界面活性劑、聚合起始劑、鏈轉移劑、{)^1調整劑並 最後將溶劑和鉗合劑加入粒種乳膠中，反應係在足夠壓力 、溫度及時間之適合反應條件下進行，如在大氣壓力及一 般從約20至約150°C，更佳係從約40至約80。(：之溫度下進.行 約0.5至約6小時。 此粒子的粒徑係從約9〇至約5〇〇毫微米，較佳係從約5〇 至約300毫微米，其中聚合物的用量係從約5至約95重量％ ’丙稀酸系或乙烯系樹脂的用量係從約95至約5重量％。乳 化聚合反應可依照標準方法完成：從一開始利用單體分散 液進行之批次聚合反應；半連續聚合反應，其中連續戒分 批餵入部分單體混合物；及連續聚合反應，其中在反應期 〇 \90\90872 DOC4 -17- 。亥樹月曰，®為離子或可離子化基，如績酸化基已存在於單 體上。此外，因為最好聚合離子或可離子化基，其沿聚合 物鏈之分布可容易地藉由技術中已知慣用方式，如注射添 加、連續進料、晚添加及類似方式控制。因此，可比先前 更奋易控制所得離子或可離子化基纟聚合物推纟物所形成 隔膜中之分布。因此，可達到各種性質如均化度、亂度、 非均化度及類似性質的調整。 此外，由於上述這些各項優點，本發明申請案可包括， 但不限於隔膜、燃料電池、塗料、離子交換樹脂、油回收 、生物隔膜、蓄電池及類似物。 聚合物離子隔膜或聚電解質隔獏可由本發明聚合物製成 。聚合物離子隔膜可由慣用薄膜製備方法製得，如溶化擠 壓、溶劑澆鑄、乳膠膠澆鑄及類似方法。隔膜電極套組可 由本發明隔膜及可用於製備隔膜電極套組之燃料電池製成 。利用本發明聚合物形成隔膜時，就聚合物中所存在之離 子丙稀酸系或乙烯基樹脂而言，聚合物可具有任何當量， 較佳係其當量為從約200至約4,000，較佳係從約2〇〇至約 1，500，極佳係從約200至約1,400。 更詳細地’本發明組合物在燃料電池、蓄電池及類似物 上是特別有用的。燃料電池及蓄電池中所用設計或組份將 與慣用燃料電池及蓄電池相同，除了利用本發明組合物形 成聚合物離子交換隔膜之外。因此，本發明可使用如美國 專利第5,795,668號和PCT公告案WO 98/22989以及W〇 98/20573中所述製造燃料電池及蓄電池的設計及方式並將 0 \90\90872 OOC4 •20- 1343143 其全文以引用方式完整地併入本文中。此隔膜可單獨使用 或與慣用填料’如矽石及類似物一起使用。燃料電池可使 用液態或氣態燃料如液態烴如甲醇。本發明燃料電池可在 寬廣操作條件範圍下操作。本發明燃料電池可具有多孔支 樓層及離子交換樹脂，其中該離子交換樹脂係受載於多孔 支標層至少一側上。本發明可用於直接曱醇燃料電池或其 他燃料電池中。較佳地，本發明燃料電池具有低燃料交又 污染、高導電率及/或高機械強度。隔膜厚度可能是慣用的 ’但最好是從約1至約1 〇密耳，較佳係從約3密耳至約5密耳 。此外，隔膜的當量最好是從約200至約2,500，較佳係約 200至約1，4〇〇。多孔支撐層可由任何慣用材料如含氟聚合 物或其他含烴聚合物如聚烯烴製成。多孔支撐層具有孔徑 '孔隙率及厚度相關慣用參數。本發明燃料電池最好具有 極佳電性質及極低電阻。 藉由下列實例使本發明更清楚，其中這些實例係被解釋 成本發明純示範例。 實例 在所有表中，除非另外指示，單體量係以重量份數表示。 本發明組合物係利用下列材料及反應條件製得： 原料 無另外純化地使用單體（ATOFINA化學試劑公司，Aci^ex®. However, non-perfluorinated polyelectrolyte membranes are rarely described in the literature. This is due to the fact that the chemical resistance, electrochemical resistance and mechanical strength of the separator are important for the application of fuel cells. In fact, the diaphragm is often at a high level [below and when the S diaphragm is very thin (less than 50 microns), the mechanical strength becomes important. For fuel cell or battery applications, the separator is in a very acid medium at temperatures up to 200 t and in the presence of metal ions, solvents and the like, thus requiring high chemical resistance and electrochemical resistance. When using a bismuth base, 'the fluorinated substance is inherently chemically resistant and chemically resistant', so these requirements are often met. However, these diaphragm displays include, but are not limited to, high mechanical properties at high temperatures (70, _200t: range), 'contamination and contamination, and mechanical failure after repeated water absorption-dehydration cycles. In addition, the preparation of these perfluorinated polyelectrolytes requires several steps and includes a chemical process that results in a high cost chemical process that will further address the fuel cell commercial barrier. The present invention relates to a non-perfluorinated polyelectrolyte comprising at least one acrylic and/or vinyl resin or polymer, wherein the resin or polymer may have at least one ion or ionizable group, such as sulfonate and/or Or phosphonated group O:\90\90872 DOC4 • 11- 1343143 A mixture of acrylic resins or may additionally contain non-acrylic resins, such as vinyl monomers and styrenic monomers β ' can be used for non-perfluorinated polyelectrolytes Examples of vinyl monomers include, but are not limited to, styrene, vinyl acetate, vinyl ether, vinyl esters such as VeoVa 9 and Ve〇Va 1® available from the shell, vinyl acrylate, vinyl pivalate, benzene. Vinyl carrate, vinyl stearate and the like and any combination thereof. Further, the non-perfluorinated polyelectrolyte comprises at least one ion (e.g., a acid salt or a phosphonate) or an ionizable group such as a sulfonated or phosphonated group or a sulfonyl group. The ionizable group is a group capable of forming an ionic group such as a cyclic amino acid, an intramineral, a maleic acid needle, a mercaptan, a sulfide, a ph〇Sphaiane, and the like. These groups may be incorporated as part of a non-perfluorinated polyelectrolyte by any means such as the incorporation of an acrylic and/or vinyl based resin in the presence of one or more monomers containing an ionic or ionizable group. In another example, one or more of the monomers used to form the non-perfluorinated polyelectrolyte can comprise an ion or an ionizable group. In addition to the above-mentioned components relating to the acrylic and/or vinyl resin, the propylene sulfonium and/or ethylene sulfonium resin may additionally or alternatively form in the presence of one or more additional monomers as long as these monomers are compatible with The integrally formed acrylic and/or vinyl based resins are compatible, wherein these additional monomers are optionally of any functional group type. As described earlier, 'the best acrylic and/or vinyl resin is the result of polymerization of several monomers, one of which contains an ionic or ionizable group, and the other contains an acrylic based on an acrylic and/or vinyl resin. And / or ethylene units. More preferably, the acrylic and/or vinyl resin is (1) alkyl acrylate 0 \ 90 \ 908 2 D 〇 C4 - 13 - 1343 143 Examples include isobutyl methacrylamide, decyl glycerol Ester, diethylene glycol dimethacrylate and trimethoxydecane methacrylate. It may be desirable to crosslink for better mechanical properties and solvent resistance. Low molecular weight copolymerizable polymers or polymerases can be utilized for certain specific applications. Further, when a mixture of the alkyl acrylate (1) and the alkyl methacrylate (2) is used, the ratio thereof can be appropriately adjusted to achieve the desired properties. Examples of monomers (5) comprising at least one ionic or ionizable group include, but are not limited to, propylene terephthalic acid propyl acrylate, vinyl phosphonic acid, ethyl benzyl acid, propyl methacrylate, fluorenyl The ethyl acrylate acid is preferably an acid form or a salt derivative of these monomers. For example, in the seed emulsion polymerization, the sulfonated monomer may be incorporated in the first stage or the second stage or both stages. The ion group content is preferably from about 200 to about 2,500 Å, preferably from about 2 Torr to about 1,100 Å, wherein EW is equivalent and is the number of grams of polymer per sulfonated unit. The present invention comprises at least one acrylic or vinyl resin or a polymer of the two preferably having an equivalent weight of acrylic or vinyl resin of from about 2 Torr to about 4,000 Å, preferably from about 2 Torr to about ι. 4〇〇, wherein the polymer has at least one ion or ionizable group. This preferred range of equivalents provides better membrane forming properties and the ability to avoid fluoropolymer requirements. The polymers of the present invention may be formed as a blend, as appropriate. Preferably, the polymers of the present invention are crosslinked using conventional cross-linking techniques. Crosslinking can be accomplished via conventional methods including, but not limited to, self-condensation, addition of a second crosslinking agent, or radiation crosslinking. These lines are fully described in the literature and are known to the art. Examples of monomers which can be subjected to self-condensation crosslinking include hydrazine-hydroxymethyl O:\90\90872. DOC4 -15- acrylamide, isobutoxy decyl acrylamide, N-methylene bis decyl decylamine And hydrazinyl dehydroglyceryl ester. Examples of the second crosslinking agent include isocyanate, dimeric decylamine, epoxide, carboxylate, alkoxydecane, anthrone, hydrazine % propane, and carbodiimide. Examples of radiation crosslinking include electron beams, ultraviolet light, and gamma rays. The polymerization of the s hydrated vinyl and/or acrylic monomer mixture can be carried out separately and then blended with one or more polymers or in the presence of one or more polymers. The polymerization of the vinyl-containing and/or acrylic monomers can be achieved by solution, bulk, emulsion polymerization or any other known polymerization method. If the polymerization of a monomer mixture containing a polymerizable ethyl bake group and/or a bupropionate ion is carried out separately and then blended with one or more polymers, the blending can be carried out by various conventional means including However, it is not limited to solution blending, extrusion blending, latex blending, and the like. For solution blending, the polymer can be dissolved or dispersed in a solvent. The solvent used for the polymer may be similar or different from the solvent used for the acrylic/vinyl ion-containing polymer. For example, the blending may comprise two solvent solutions/dispersions or the addition of the powder to the solvent solution/dispersion or the two polymers may be dissolved in the same solvent or any other composition. Typical solvents used include tetrahydrofuran, acetone, dimethyl sulfite, dimethyl mercaptoamine, hydrazine-methylpyrrolidone. For melt extrusion blending, typical extrusion temperatures range between about 1 Torr and about 30 (TC, preferably from about yo ° C to about 250 ° C. The material can be extruded into particles such as granules. Or film shape. For latex blending examples, mixing can be achieved in several conventional ways: acrylic/vinyl latex can be mixed with polymer latex or acrylic/ethylene polymer 〇\90\90872.DOC4 • 16-1343143 can be dispersed or dissolved in polymer latex or any other known mixing method a can contain more than two types of latex. The amount and nature of each latex is adjusted according to the expected physical and chemical properties and the expected EW. In the case of aqueous membranes (such as those made by direct latex), the particle size and solids content of one or more latexes can be adjusted for the desired properties. For solvent polymerization, the polymerization can take place using conventional techniques. In the case of a blend of polymers, the solvent used for the polymer blend may be similar or different from the solvent used for the acrylic/vinyl polymer. For example, blending may include two solvent solutions/dispersions or powders. It is typically used in a solvent solution/dispersion or in the presence of two polymers in the same solvent or in any other composition; the granules include dimercapto, hard dimethyl ketone, Ν·methyl 嘻 嘻, Isopropanol, methanol and similar solvents. Emulsification polymerization can be carried out under the same conditions as conventional emulsion polymerization. It is preferred to use a surfactant, a polymerization initiator, a chain transfer agent, a modifier, and finally a solvent. The chelating agent is added to the granule latex and the reaction is carried out under suitable reaction conditions of sufficient pressure, temperature and time, such as at atmospheric pressure and generally from about 20 to about 150 ° C, more preferably from about 40 to about 80. (: at a temperature of about 0.5 to about 6 hours. The particle size of the particles is from about 9 Å to about 5 Å, preferably from about 5 Å to about 300 nm, wherein the polymer The amount is from about 5 to about 95% by weight of the 'acrylic acid or vinyl resin is from about 95 to about 5% by weight. The emulsion polymerization can be carried out according to standard methods: from the beginning using a monomer dispersion Batch polymerization; semi-continuous polymerization in which a part of the monomer mixture is fed continuously or batchwise; and continuous polymerization, wherein during the reaction period 〇\90\90872 DOC4 -17-. An ionizable group, such as an acidifying group, is already present on the monomer. Further, since the polymerized ion or the ionizable group is preferred, its distribution along the polymer chain can be easily carried out by conventional methods known in the art, such as injection. Addition, continuous feeding, late addition, and the like control. Therefore, it is possible to control the distribution in the separator formed by the obtained ion or the ionizable base polymer pusher more than before. Therefore, various properties such as homogenization can be achieved. Degree, disorder, non-uniformity and Adjustments of similar properties. Further, due to the above advantages, the present invention may include, but is not limited to, separators, fuel cells, coatings, ion exchange resins, oil recovery, biological separators, batteries, and the like. Alternatively, the polyelectrolyte barrier can be made from the polymer of the present invention. The polymeric ion barrier can be made by conventional thin film preparation methods such as melt extrusion, solvent casting, latex casting, and the like. The membrane electrode set can be made from the separator of the present invention. For the preparation of a fuel cell for a diaphragm electrode set. When the separator is formed by using the polymer of the present invention, the polymer may have any equivalent amount, preferably a unit, in terms of an ionic acrylic acid or a vinyl resin present in the polymer. The equivalent weight is from about 200 to about 4,000, preferably from about 2 to about 1,500, and most preferably from about 200 to about 1,400. More specifically 'the composition of the invention in fuel cells, batteries, and the like It is particularly useful. The design or components used in fuel cells and batteries will be the same as conventional fuel cells and batteries, except that the present invention is utilized. The formation of a fuel cell and a battery is described in the context of the invention. 0 0 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 Such as a liquid hydrocarbon such as methanol. The fuel cell of the present invention can be operated under a wide range of operating conditions. The fuel cell of the present invention can have a porous support floor and an ion exchange resin, wherein the ion exchange resin is supported on at least one side of the porous support layer. The invention can be used in direct methanol fuel cells or other fuel cells. Preferably, the fuel cell of the present invention has low fuel cross-contamination, high electrical conductivity and/or high mechanical strength. The thickness of the membrane may be conventional 'but preferably from about 1 to about 1 mil, preferably from about 3 mils to about 5 mils. Further, the equivalent weight of the separator is preferably from about 200 to about 2,500, preferably from about 200 to about 1,4 Torr. The porous support layer can be made of any conventional material such as a fluorine-containing polymer or other hydrocarbon-containing polymer such as polyolefin. The porous support layer has a pore size 'porosity and thickness related conventional parameters. The fuel cell of the present invention preferably has excellent electrical properties and extremely low electrical resistance. The invention is further clarified by the following examples, which are to be construed as a pure example of the invention. EXAMPLES In all tables, monomer amounts are expressed in parts by weight unless otherwise indicated. The composition of the present invention is obtained by the following materials and reaction conditions: Raw materials The monomer is used without additional purification (ATOFINA Chemical Reagent Co., Ltd.,

Aldrich)、起始劑（Aldrich，DuPont)、界面活性劑（Aldrich) 及緩衝液（Aldrich)。 反應 O:\90\90872 DOC4 -21- 1343143 預先將過硫酸銨0.3克、月桂基硫酸鈉1克及去離子水300 克裝入500毫升裝有冷凝器、高純度氮氣及單體入口和機械 攪拌器之四頸鍋中。將反應器加熱高達65°C並以所需速率 利用針筒式泵浦將單體混合物[曱基丙烯酸甲酯（MMA) 46 克及甲基丙烯酸磺酸丙酯9克]送入反應器中。視情況可在 反應期間之前，將一部分單體混合物加入預載物中。然後 藉保持反應溫度並攪拌1 20分鐘以聚合剩餘單體。然後，將 媒介冷卻至室溫、排氣並經紗布過濾最終分散液。最終固 體含量為15重量％。 表1 : 包含磺酸化單體之樹脂的代表性合成樹脂 實例 MMA TPMS BA S IBMA HEMA SPM EW 1 56.6 24 2.2 17.2 1140 2 40 39 2.4 18.5 1330 3 28.6 19 19 9.5 23.8 1035 4 31.5 21.1 21.1 10.5 15.8 1560 5 28.6 19 19 9.5 23.8 1035 6 31.7 21 21 10.5 15.8 1560 7 31.6 21 21 10.5 15.8 1535 8 39.9 39.2 2.4 18.5 1330 9 37.8 3.4 11.8 27.5 19.5 1266 10 33 32.5 2 32.5 758 0 \9〇\g〇872.DOC4 -22- 表2 : 質子導電率測量之實例 實例 澆鑄類型 質子導電率 来 5 乳膠澆鑄 25 6 乳膠澆鑄 34 7 乳膠澆鑄 *---- 22 8 乳膠澆鑄 13 9 溶液澆鑄 20 10 溶液澆鑄 60 2 溶液澆鑄 9 1343143 實驗： 導電率測量係藉電化學阻抗頻譜分析儀以四探針構型完 成。測量係以Gamry儀器（電位儀-Galvanostat zrapC4/750 及EIS 300軟體）在5X105與1 Hz之間進行。在此所示值係在 室溫下浸沒條件下獲得。 調配物的製備如下： 進行乳膠之調配如下： 將2克Baybond 116及1克Acrysol 275溶於4克丁讀中。溶 液與2克TEP混合，在固定攪拌下將所得溶液緩慢地加入1〇〇 克乳膠中。 利用刮刀型塗佈器將薄膜澆鑄在玻璃基板上並在烘箱中 範圍從80C至l〇〇C之溫度下固化1至Η分鐘。 溶劑調配物的製備如下： 乾燥丙烯酸系乳膠並回收所得粉末。然後，將1 〇至2〇克 〇 ^90872 DOC4 -23-Aldrich), starter (Aldrich, DuPont), surfactant (Aldrich) and buffer (Aldrich). Reaction O:\90\90872 DOC4 -21- 1343143 Pre-added 0.3 g of ammonium persulfate, 1 g of sodium lauryl sulfate and 300 g of deionized water into 500 ml equipped with condenser, high purity nitrogen and monomer inlet and machinery The four-neck pot of the blender. The reactor was heated up to 65 ° C and the monomer mixture [methyl methacrylate (MMA) 46 g and propyl methacrylate sulfonate 9 g] was fed into the reactor at the desired rate using a syringe pump. . Optionally, a portion of the monomer mixture can be added to the preload before the reaction period. The remaining monomer was then polymerized by maintaining the reaction temperature and stirring for 1 20 minutes. The medium was then cooled to room temperature, vented and the final dispersion was filtered through gauze. The final solid content was 15% by weight. Table 1: Examples of representative synthetic resins of resins containing sulfonated monomers MMA TPMS BA S IBMA HEMA SPM EW 1 56.6 24 2.2 17.2 1140 2 40 39 2.4 18.5 1330 3 28.6 19 19 9.5 23.8 1035 4 31.5 21.1 21.1 10.5 15.8 1560 5 28.6 19 19 9.5 23.8 1035 6 31.7 21 21 10.5 15.8 1560 7 31.6 21 21 10.5 15.8 1535 8 39.9 39.2 2.4 18.5 1330 9 37.8 3.4 11.8 27.5 19.5 1266 10 33 32.5 2 32.5 758 0 \9〇\g〇872.DOC4 -22- Table 2: Example of proton conductivity measurement Example casting type proton conductivity to 5 Latex casting 25 6 Latex casting 34 7 Latex casting *---- 22 8 Latex casting 13 9 Solution casting 20 10 Solution casting 60 2 Solution Casting 9 1343143 Experiment: Conductivity measurement was performed in a four-probe configuration by an electrochemical impedance spectrum analyzer. The measurement was performed with a Gamry instrument (potentiometer - Galvanostat zrap C4/750 and EIS 300 software) between 5X105 and 1 Hz. The values shown here are obtained under immersion conditions at room temperature. The formulation was prepared as follows: The latex was formulated as follows: 2 grams of Baybond 116 and 1 gram of Acrysol 275 were dissolved in 4 grams of reading. The solution was mixed with 2 g of TEP, and the resulting solution was slowly added to 1 g of the latex under fixed stirring. The film was cast on a glass substrate using a doctor blade type applicator and cured in an oven at a temperature ranging from 80 C to 10 C for 1 to Η minutes. The solvent formulation was prepared as follows: The acrylic latex was dried and the resulting powder was recovered. Then, 1 〇 to 2 〇 〇 ^90872 DOC4 -23-

Claims (1)

1343143 第093102930號專利申請案 中文申請專利範圍替換本(99年12月） 拾、申請專利範圍的if人 1. 一種包含非全氟化聚電解質之隔膜，其中該非全氟化聚 電解質包含至少-種具有至少—個離子基或可離子化基 之丙烯酸系、樹脂或乙缔基樹脂或其兩者，其中該非全氟 化ΛΚ電解貝不含氟聚合物，其中該離子基或可離子化基 為續酸化基或膦酸化基或其兩者，其中該丙烯酸系樹脂 或乙烯基樹脂或其兩者包含至少一具有可交聯之官能基 的可共聚合單體，其中該隔膜係已交聯，且其中該可共 聚合單體包含異丁基甲基丙烯醯胺、曱基丙烯酸去水甘 油S曰一甲基丙烯酸二乙二醇酯或三曱氧基矽烷曱基丙 烯酸酯。 2. 如申請專利範圍第丨項之隔膜，其中該非全氟化聚電解質 在交聯前具有約200至約4,〇〇〇之當量（EW)。 3‘如申請專利範圍第旧之隔膜，其中該非全氣化聚電解質 在交聯前具有約200至約ι，5〇〇之當量。 90872-991215.doc1343143 Patent Application No. 093102930, Chinese Patent Application Serial No. (December 99), the patent of the patent application, 1. A separator comprising a non-perfluorinated polyelectrolyte, wherein the non-perfluorinated polyelectrolyte comprises at least An acrylic, resin or ethylenic resin having at least one ionic or ionizable group, or both, wherein the non-perfluorinated cerium electrolysis is not a fluoropolymer, wherein the ionic or ionizable group Or a phosphorylated group or both, wherein the acrylic resin or vinyl resin or both comprise at least one copolymerizable monomer having a crosslinkable functional group, wherein the separator has been crosslinked And wherein the copolymerizable monomer comprises isobutylmethacrylamide, dehydrazinyl hydrazide S?-diethylene glycol diethylene glycol or tridecyloxydecane methacrylate. 2. The separator of claim 3, wherein the non-perfluorinated polyelectrolyte has an equivalent weight (EW) of from about 200 to about 4, prior to crosslinking. 3 'As in the case of the oldest membrane of the patent application, wherein the non-fully gasified polyelectrolyte has an equivalent weight of from about 200 to about 10,5 Å before crosslinking. 90872-991215.doc
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